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US4042645A - Process for producing thermosetting finishing powders - Google Patents

Process for producing thermosetting finishing powders Download PDF

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Publication number
US4042645A
US4042645A US05/426,954 US42695473A US4042645A US 4042645 A US4042645 A US 4042645A US 42695473 A US42695473 A US 42695473A US 4042645 A US4042645 A US 4042645A
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weight
polymerization
copolymer
monomers
solid
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US05/426,954
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Kuniomi Hirota
Akio Masumoto
Hiroshi Ozawa
Nobuki Kobayashi
Teruo Honda
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Mitsui Toatsu Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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Priority claimed from JP9464269A external-priority patent/JPS4837748B1/ja
Priority claimed from JP1148270A external-priority patent/JPS4838618B1/ja
Application filed by Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Priority to US05/426,954 priority Critical patent/US4042645A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31699—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a process for producing thermosetting finishing powders to be used in coating processes in powder form. More particularly, the present invention relates to a process for producing a thermosetting finishing powder which is high in thermal fluidity during baking when applied as a coating to such base materials as metal and is very high in such properties as thermal stability, resistance to solvents, metal adhesion, mechanical strength and durability against weathering when it has been thermoset.
  • the resin ingredients most conventionally used today for finishing powders typically include vinyl chloride resins or epoxy resins.
  • these resins exhibit defects which tend to greatly restrict their practical use in paints.
  • the vinyl chloride type finishing powders are thermally unstable due to the dehydrochlorination of vinyl chloride, are so thermoplastic that they have low resistance to solvents and adhere so poorly to metals that a primer must be used in most cases.
  • the epoxy resin type finishing powders are made by using a curing agent such as a polyamide, polyamine or acid anhydride, but are so low in durability to weathering that they cannot be used for out-of-doors applications.
  • thermoplastic solid acrylic resins wherein the reactive monomers are not copolymerized, even if a cross-linking agent is added, a three-dimensional cross-linked structure cannot be obtained and the resin remains in a two-dimensional linear structure. Therefore, in order to maintain mechanical strength and resistance to solvents which will endure during practical use it has been necessary to greatly increase the molecular weight. However, in general, in order for the resin to be practically used as a finishing powder, it is most important that the resin has high thermal fluidity. If the molecular weight of the thermoplastic acrylic resin is reduced in order to obtain the high thermal fluidity, the mechanical strength and resistance to solvents are also greatly reduced and no practicable finishing powders are obtained.
  • thermosetting acrylic resins are extensively used in solution-type paints which are made by including an aminoformaldehyde resin or epoxy resin as a cross-linking agent.
  • thermosetting acrylic resins are not advantageously used as resins for a finishing powder.
  • a conventional thermosetting acrylic resin is used for a finishing powder, it is very difficult to initiate a cross-linking reaction after the powder is heated to a fluid state and a smooth thermoset painted surface is not obtained.
  • Another reason is that it is substantially difficult to produce a solid thermosetting acrylic resin which can be used for a finishing powder in a form containing no volatile ingredient.
  • thermoplastic acrylic solid resins include bulk-polymerization, suspension-polymerization and emulsion-polymerization.
  • a thermosetting acrylic solid resin which can be used as a finishing powder is difficult to produce by any of these known polymerization processes.
  • thermosetting acrylic when a thermosetting acrylic is used in formation of a powdery thermosetting solid coating composition, unlike the case where it is used as a molding material, the weight average molecular weight (Mw) should not exceed about 100,000 and, by correlation, the number average molecular weight (Mn) should not exceed about 30,000.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the thermal fluidity or flowability is so low that the resin cannot be put into practical use. In that case, such a large amount of polymerization initiator is required that when attempting production by the bulk polymerization process, it is difficult to control the heat generated by the polymerization.
  • the suspension-polymerization process When attempting production by the suspension-polymerization process, since the functional groups of the monomer impart high water-solubility, it is difficult to complete the polymerization while maintaining stability of the suspension state; therefore the suspension-polymerization process cannot be adopted to any great extent.
  • the emulsifier is mixed into the painted film and a weather proof painted film cannot be obtained.
  • thermosetting finished powders wherein a solid thermosetting acrylic resin is used.
  • thermosetting finishing powders which exhibit high thermal fluidity.
  • thermosetting finishing powders which overcome the deficiencies in thermal stability, resistance to solvents and adhesion to metals exhibited by vinyl chloride type resins.
  • thermosetting finishing powders which overcome the deficiency in durability to weathering exhibited by epoxy type resins.
  • thermosetting finishing powders which overcome the deficiencies in mechanical strength and resistance to solvents exhibited by thermoplastic acrylic resins.
  • One embodiment of the present invention includes a process for producing solid copolymers (a) having a glass transition point of from 5° to 60° C. and a number average molecular weight of from 1,500 to 30,000 by bulk-polymerizing a monomer mixture consisting of a cross-linkable monomer having the structure: ##STR2## wherein R 1 is H or CH 3 and R 2 is an alkyl radical containing from 1 to 14 carbon atoms, in an amount at least 30% by weight based on the total monomers to be copolymerized, an ethylenic ⁇ , ⁇ unsaturated carboxylic acid monomer in an amount from 3 to 20% by weight based on the total monomers to be copolymerized and 0 to 67% by weight based on the total monomers to be copolymerized of a monomer copolymerizable with each of the above monomers, until conversion to the polymer is from 10 to 80% by weight and then adding a polymerization initiator and completing the polymerization by suspension-
  • Another embodiment of the present invention includes a process for producing solid copolymers (b) having a glass transition point of from 5° to 60° C. and a number average molecular weight of from 1,500 to 30,000 by bulk-polymerizing a monomer mixture consisting of a cross-linkable monomer having the structure: ##STR3## wherein R 1 is H or CH 3 and R 2 is an alkyl radical of containing from 1 to 14 carbon atoms, in an amount at least 30% by weight based on the total monomers to be copolymerized, a monomer having the structure: ##STR4## wherein R 1 is H or CH 3 , in an amount from 3 to 40% by weight based on the total monomers to be copolymerized and a monomer copolymerizable with each of the above monomers in an amount of 0 to 67% by weight based on the total monomers to be copolymerized until conversion to the polymer is from 10 to 80% by weight and then adding a polymerization initiator and completing the
  • thermosetting finishing powder is produced by mixing 40 to 5 parts by weight of an epoxy resin containing 2 or more epoxy radicals in the molecule and from 0.02 to 2.0 parts by weight of a tertiary amine having the structure: ##STR5## wherein each of R 1 , R 2 and R 3 is alkyl containing from 1 to 8 carbon atoms or phenyl, or a derivative thereof, as a curing accelerator, with 60 to 95 parts by weight of the solid copolymer (a) produced by the above described process and then crushing the mixture to a powder.
  • thermosetting finishing powder is produced by mixing 40 to 3 parts by weight of a cross-linking compound containing 2 or more equivalents of carboxyl radicals or acid anhydrides thereof in the molecule or 40 to 3 parts by weight of a cross-linking compound containing in the molecule at least 2 nitrogen atoms having adjacent thereto at least one active hydrogen (and thus containing at least two structures having the formula: ##STR6## wherein one or both of R 1 and R 2 is hydrogen) with 60 to 97 parts by weight of the solid copolymer (b) produced by the respective above described process.
  • the monomers which have the general formula: ##STR7## wherein R 1 is H or CH 3 and R 2 is an alkyl radical containing from 1 to 14 carbon atoms, which are used to produce solid copolymers (a) and (b) by the above-described processes of the present invention include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and tridecyl methacrylates.
  • thermosetting solid coating composition impart excellent thermal stabilty and weatherability to the resulting thermosetting solid coating composition and at least one is used in the present invention.
  • amount of said monomer used is less than 30% by weight based on the total monomers to be copolymerized, the durability against weathering, metal adhesion and thermal stability of the obtained finish are reduced.
  • the ethylenic ⁇ , ⁇ unsaturated carboxylic acid monomers used in the above described process to obtain solid copolymer (a) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic anhydride. These monomers react with the epoxy resin to cause thermosetting and improve solvent resistance of the resulting thermosetting solid coating composition and at least one of the monomers is used. If the amount of said ethylenic ⁇ , ⁇ unsaturated carboxylic acid monomer used is less than 3% by weight based on the total monomers to be copolymerized, it does not measurably contribute to an improvement of solvent resistance and mechanical strength.
  • the amount exceeds 20% by weight, the thermal fluidity is reduced and no smooth painted surface is obtained. Also, in this instance, the monomer would tend to react with the epoxy resin during mixing by melt-kneading to cause undesired gelation.
  • the finishing powder it is very important for the practical use of the finishing powder to limit the ranges of the glass transition point and the number average molecular weight. If the glass transition point is below 5° C., the produced finishing powder tends to be sticky and cohere and therefore cannot be used in practice. When it exceeds 60° C., the thermal fluidity is too low for practical use. Further, if the number average molecular weight is less than 1500, the solvent resistance and mechanical strength are reduced. When it exceeds 30,000, the thermal fluidity becomes so low that a smooth painted surface is not obtained.
  • the monomers copolymerizable with each of the above described monomers include, for example, styrene, ⁇ -methyl styrene, vinyl toluene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ⁇ -hydroxyethyl acrylate and ⁇ -hydroxypropyl methacrylate.
  • styrene ⁇ -methyl styrene
  • vinyl toluene vinyl chloride
  • vinylidene chloride acrylonitrile
  • methacrylonitrile vinyl acetate
  • vinyl propionate ⁇ -hydroxyethyl acrylate
  • the amount of these monomers must also satisfy the limiting conditions of the glass transition point and number average molecular weight of the resultant copolymers.
  • the mixture of the monomers is copolymerized at a temperature of from 80° to 150° C., preferably 100° to 130° C., by a bulk-polymerization process until conversion to the polymer has reached 10 to 80% by weight, then suspension-polymerization is carried out. If conversion to the polymer is less than 10% by weight, and if suspension-polymerization is then used, the cross-linkable monomers as described above are so highly water-soluble that they dissolve into the water layer and it is difficult to maintain a favorable suspension state and a solid copolymer suitable for use for the finishing powder of the present invention is not obtained.
  • the temperature adopted for the suspension polymerization will vary depending on the polymerization initiator used but in general will range between 60° and 100° C.
  • the polymerization initiators used are conventional radical polymerization initiators, for example, organic peroxides represented by benzoyl peroxide and lauroyl peroxide and azobisnitriles such as azobisisobutylonitrile.
  • the polymerization initiator is used in an amount of from 0.5 to 5.0% by weight of the total monomers to be copolymerized. However, it is possible to add a portion of the polymerization initiator in a range allowing for control of the polymerization heat in the bulk-polymerization step.
  • the polymerization initiator is effective for adjusting the number average molecular weight of the polymer obtained after completion of the suspension polymerization step of the process of the invention.
  • the number average molecular weight can be further adjusted, if necessary, between 1,500 to 30,000 by using less than 5% by weight of a chain transfer agent such as a mercaptan, for example, primary or tertiary dodecylmercaptan, a disulfide, for example, diisopropylxanthogen disulfide, a diazothioether or a halide.
  • a chain transfer agent such as a mercaptan, for example, primary or tertiary dodecylmercaptan, a disulfide, for example, diisopropylxanthogen disulfide, a diazothioether or a halide.
  • the dispersing agents used are high molecular weight organic substances such as gelatin, tragacanth, starch, methyl cellulose and carboxymethyl cellulose and synthetic high molecular weight substances such as polyvinyl alcohols, partially saponified polyvinyl alcohols, polyacrylates and polyacrylamides, inorganic salts such as BaSO 4 , CaSO 4 , CaCO 3 , MgCO 3 and Ca 3 (PO 4 ) 2 , inorganic high molecular weight substances such as talc, bentonite, silicic acid, diatomaceous earth and clay and metals and metal oxides, that are known as dispersing agents. in suspension-polymerization. Further, such known salts as NaCl. KCl and Na 2 SO 4 and surface active agents of the anionic, cationic and nonionic types may be simultaneously used as dispersing assistants.
  • high molecular weight organic substances such as gelatin, tragacanth, starch, methyl cellulose and carboxymethyl cellulose and synthetic high mole
  • a two-stage polymerization by bulk-polymerization and suspension-polymerization is used, so that the greater part of the above described cross-linkable monomers which are highly water-soluble may be introduced into the polymer chains during the bulk-polymerization step so as to be insoluble in water and therefore, in the suspension-polymerization stage, it is possible to maintain a favorable suspension state, a favorable pearly polymer which can be used substantially as a thermosetting finishing powder is obtained and it is also possible to adjust the number average molecular weight of the polymer within a range of 1,500 to 30,000.
  • thermosetting finishing powder is produced by dehydrating the copolymer, then drying it with a fluid layer dryer, air current dryer or hot-air dryer and then mixing it with such cross-linking agent to be used in the present invention as will be seen in the following.
  • Typical epoxy resins which have two or more epoxy radicals in the molecule and which are cross-linking agents to be mixed with the solid copolymer (a) obtained by the above described process are: polyvalent epoxy compounds obtained by the condensation of bisphenol A and epichlorohydrin or ⁇ -methylepichlorohydrin; polyvalent epoxy compounds obtained by the condensation of a novolak or resol and epichlorohydrin; diepoxy compounds having a polyether in the skeleton; and alicyclic epoxy compounds.
  • thermosetting finishing powder When the sum of the solid copolymer (a) and the epoxy resin cross-linking agent is considered as 100%, if the amount of the epoxy resin is less than 5%, the solvent resistance and mechanical strength of the obtained thermosetting finishing powder become poor and, if it exceeds 40% by weight, the durability against weathering is unsatisfactory. In this embodiment it is preferable to add a curing accelerator to the mixture.
  • tertiary amine curing accelerators and derivatives thereof include, for example, trimethylamine, triethylamine, triisopropylamine, dimethylbenzylamine, triethylammonium chloride, triisopropylammonium chloride, dimethylbenzylammonium chloride, triethylamine sulfonate and boron trifluoride-triethylamine complex compound. They are used preferably in an amount from 0.02 to 2.0 parts by weight per 100 parts by weight of the resin solid. The use of this amine component promotes the thermosetting reaction between the carboxylic acid of the solid copolymer (a) and the epoxy group at the time of actual application.
  • the amount of amine component is less than 0.02 part by weight, the solvent resistance of the resulting thermosetting coating composition is insufficient and if the amount exceeds 2.0 parts by weight, the viscosity increases extremely at the time of the mixing operation so that it is difficult to obtain a powdery composition and thermal stability is lowered.
  • the solid copolymer (a) and the epoxy resin are put into a heatable mixing machine such as, for example, an extruder, a co-kneader or a Henschel type mixer, and melted and mixed at a temperature in the range of 120° to 200° C.
  • a heatable mixing machine such as, for example, an extruder, a co-kneader or a Henschel type mixer, and melted and mixed at a temperature in the range of 120° to 200° C.
  • the solid copolymer (a) and the epoxy resin may be mixed and melted simultaneously, or it is possible to premelt one of the two components and then mix the melt with the second component.
  • the obtained melt is cooled, if necessary, to a temperature not exceeding 150° C. and then the curing accelerator is added and mixed therewith. When the mixture consistency becomes uniform, it is cooled and crushed.
  • the cross-linking compounds which contain two or more equivalents of a carboxyl radical or acid anhydride thereof in the molecule and which are mixed with solid copolymer (b), include such polyvalent carboxylic acid compounds as phthalic anhydride, isophthalic acid, adipic acid, succinic acid, sebacic acid, citric acid, itaconic acid, aconitic acid, maleic anhydride, fumaric acid, trimellitic anhydride, hexahydrophthalic acid, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, pimelic acid and pyromellitic anhydride, polyester resins having two or more carboxyl radicals in the molecule which are obtained by esterification of these polyvalent carboxylic acid compounds with polyhydric alcohols, and solid copolymers (a) wherein two or more ethylenic ⁇ , ⁇ unsaturated carboxylic acid monomers are copolymerized in the molecule.
  • the cross-linking compounds which contain two or more nitrogen atoms having one or two active hydrogen atoms adjacent thereto in the molecule include cyclohexylaminopropylamine, methaphenylene diamine, p,p'-diaminodiphenyl methane, p,p'-diaminodiphenyl sulfone, dicyandiamide, polyamide resins having in the molecule at least two amide groups and epoxy-amine adducts containing in the molecule at least two nitrogen atoms adjacent to an active hydrogen atom, which are obtained by reacting an amine with an epoxy resin.
  • Both of the above types of cross-linking compounds exhibit compatability with the above solid copolymer (b) when rendered molten by heating but they do not react with the copolymer to cause cross-linking before they are rendered molten. It is also necessary that they do not exhibit viscosity or stickiness when admixed with the solid copolymer (b).
  • An appropriate selection of a desired cross-linking compound having these properties is made dependent upon the composition, glass transition point and number average molecular weight of the solid copolymer (b).
  • the amount of the cross-linking agent is less than 3% by weight of the total weight of cross-linking agent and copolymer (b), no sufficient thermosetting occurs and therefore the solvent resistance and mechanical strength are low.
  • the amount exceeds 40% by weight the durability against weathering is reduced, and the thermal fluidity is greatly reduced in some cases.
  • the solid copolymer (b) and the cross-linking compound are mixed together and then crushed or ground at room temperature or below, e.g. at 0° to 30° C., to a powder, e.g. of 40 to 300 mesh.
  • the solid copolymer (b) is preferably rendered molten, e.g. by means of a kneader capable of high agitation and heating, the cross-linking compound is incorporated in the melt and the mixture is then cooled to room temperature or below, e.g. to 20° to 30° C. and crushed or ground to a powder, e.g. of 40 to 300 mesh.
  • thermosetting finishing powders of the present invention when applied as a coating may also include inorganic fillers such as titanium oxide, iron oxide, silica, calcium carbonate or barium sulfate, organic pigments such as carbon black, phthalocyanine blue or Sincasia red, modified cellulose such as cellulose acetate butyrate, methoxycellulose or ethoxycellulose, a plasticizer such as dibutyl phthalate, dioctyl phthalate or epoxidized oil or other additives such as silicone or wax. They are mixed with the powders by a dry-blending process, semi-dry-blending process or melt-blending process, and are then crushed to a powder.
  • inorganic fillers such as titanium oxide, iron oxide, silica, calcium carbonate or barium sulfate, organic pigments such as carbon black, phthalocyanine blue or Sincasia red, modified cellulose such as cellulose acetate butyrate, methoxycellulose or ethoxycellulose, a plasticizer such as dibutyl
  • thermosetting finishing powder produced by the above described method is applied as a coating on a base material such as a metal and is then baked for from 5 to 60 minutes within a dryer at 160° to 220° C. to obtain a thermoset painted film which is high in thermal fluidity during baking and is excellent in thermal stability, solvent resistance, metal-adhesion, mechanical strength and durability against weathering.
  • Examples 1 and 2 show a process for using a solid copolymer obtained by copolymerizing an ethylenic ⁇ , ⁇ unsaturated carboxylic acid monomer in producing a thermosetting finishing powder.
  • the polyvinyl alcohol used had a saponification degree of 80%. While the reaction product was kept suspended, suspension-polymerization was carried out at the temperatures and times shown in Table I. The obtained product was washed with water and dried with a vacuum dryer to obtain a pearly copolymer having a grain diameter of 50 to 150 meshes per inch. The glass transition points and number average molecular weights of the respective obtained copolymers are also shown in the table.
  • thermosetting finishing powders were produced by the following process.
  • the solid copolymer and titanium oxide were put into a Henschel type mixer, and were melted and blended according to the conditions shown in Table 2. Then the epoxy resin shown in the table was mixed therewith. After the melted mixture was cooled to a temperature of from 110° to 120° C., the curing accelerator shown in the table was mixed therewith. Then the melted mixture was immediately cooled and was crushed with a crusher. The powder passing through a sieve of 150 meshes per inch was collected to produce a thermosetting finishing powder shown in each of Runs 1-7 in the table. All of the numerical values in the table with the exception of the blending temperatures indicate parts by weight.
  • thermosetting finishing powders 1 to 7 On steel plates of a thickness of 0.8 mm. treated with zinc phosphate each of the thermosetting finishing powders 1 to 7 shown in the above table and such controls as an epoxy resin finishing powder, vinyl chloride resin finishing powder and thermoplastic acrylic resin finishing powder were painted with an electrostatic powder coating machine and then baked for 20 minutes in a hot-air dryer adjusted to a temperature of 200° C. The obtained respective test plates were evaluated respective to the characteristics of each painted film on the test plates. The results are collectively shown in the table. Tested powders 1-7 represent the present invention and the remaining powders are prior art powders for control and comparison purposes.
  • Examples 3 and 4 show a process for using a solid copolymer obtained by copolymerizing a glycidyl acrylate or glycidyl methacrylate monomer in producing a thermosetting finishing powder.
  • the reaction product was cooled and then agitated with addition of the amounts of polymerization initiator, dispersing agent and ion exchanged water shown in the table. While the product was kept suspended, suspension-polymerization was carried out under the conditions shown in the table. The obtained product was washed with water and then dried with a vacuum dryer to obtain a pearly copolymer having a grain diameter of 50 to 150 meshes per inch. The glass transition points and number average molecular weights of the respective obtained polymers are also shown in the table.
  • the polyvinyl alcohol used had a saponification degree of 80%.
  • the solid copolymers F-I obtained in Example 3 were made into thermosetting finishing powders by the following method.
  • the solid copolymer and titanium oxide were put into a Henschel type mixer and were melted and mixed according to Run Nos. 8-13 shown in the following Table V. Then a cross-linking agent as shown in the table was mixed into the melted mixture. When a curing accelerator was added, it was mixed after the melted mixture was cooled to a temperature in the range of 100° to 120° C.
  • thermosetting finishing powders All the numerical values in the table with the exception of the blending temperature indicate parts by weight.
  • thermosetting finishing powders obtained by the present invention and described in Runs 8-13 of Example 4 are shown in the following Table VI.
  • the thermosetting finishing powders 8-13 and an epoxy resin finishing powder, vinyl chloride resin finishing powder and thermoplastic acryl resin finishing powder for comparison purposes were painted with an electrostatic powder painting apparatus onto steel plates, having a thickness of 0.8 mm. and treated with zinc phosphate, and were further baked for 20 minutes with a hot-air dryer adjusted to a temperature of 200° C. to obtain the respective test plates. The results are collectively shown in the table.
  • the finishing powders used for comparison and the testing methods were the same as used in Example 2 and as shown in Table III.

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Abstract

Solid copolymers are produced by copolymerizing a mixture of: (A) at least 30% by weight of a monomer having the formula: ##STR1## wherein R1 is H or CH3 and R2 is an alkyl radical containing from 1 to 14 carbon atoms; (B) from 3 to 20% by weight of an ethylenic α, β unsaturated carboxylic acid or anhydride thereof, or from 3 to 40% by weight of glycidyl acrylate or glycidyl methacrylate; and (C) from 0 to 67% by weight of a monomer copolymerizable with said monomers (A) and (B). Preferably, the mixture is first bulk-polymerized until conversion to the copolymer is from 10 to 80% by weight and the polymerization is completed by suspension-polymerization. Thermosetting solid coating compositions are produced by mixing a major proportion of a solid copolymer so produced with a minor proportion of a cross-linking compound or with an epoxy resin containing at least 2 epoxy radicals in the molecule in presence of a tertiary amine curing accelerator.

Description

CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of Serial No. 91,197 filed Nov. 19, 1970, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing thermosetting finishing powders to be used in coating processes in powder form. More particularly, the present invention relates to a process for producing a thermosetting finishing powder which is high in thermal fluidity during baking when applied as a coating to such base materials as metal and is very high in such properties as thermal stability, resistance to solvents, metal adhesion, mechanical strength and durability against weathering when it has been thermoset.
2. Description of the Prior Art.
In the coating of metals and the like, solvent-type paints made by dispersing synthetic resins and pigments in solvents, water-soluble paints and emulsion paints have been extensively used. Recently a technique for coating paint in the form of a powder free from such volatile ingredients as solvent or water by an electrostatic coating method or fluidized bed process has been developed and has been practiced to a certain extent.
The resin ingredients most conventionally used today for finishing powders typically include vinyl chloride resins or epoxy resins. However, these resins exhibit defects which tend to greatly restrict their practical use in paints. For example, the vinyl chloride type finishing powders are thermally unstable due to the dehydrochlorination of vinyl chloride, are so thermoplastic that they have low resistance to solvents and adhere so poorly to metals that a primer must be used in most cases. On the other hand, the epoxy resin type finishing powders are made by using a curing agent such as a polyamide, polyamine or acid anhydride, but are so low in durability to weathering that they cannot be used for out-of-doors applications.
In thermoplastic solid acrylic resins wherein the reactive monomers are not copolymerized, even if a cross-linking agent is added, a three-dimensional cross-linked structure cannot be obtained and the resin remains in a two-dimensional linear structure. Therefore, in order to maintain mechanical strength and resistance to solvents which will endure during practical use it has been necessary to greatly increase the molecular weight. However, in general, in order for the resin to be practically used as a finishing powder, it is most important that the resin has high thermal fluidity. If the molecular weight of the thermoplastic acrylic resin is reduced in order to obtain the high thermal fluidity, the mechanical strength and resistance to solvents are also greatly reduced and no practicable finishing powders are obtained.
Today conventional thermosetting acrylic resins are extensively used in solution-type paints which are made by including an aminoformaldehyde resin or epoxy resin as a cross-linking agent. However, for several reasons, thermosetting acrylic resins are not advantageously used as resins for a finishing powder. For example, when a conventional thermosetting acrylic resin is used for a finishing powder, it is very difficult to initiate a cross-linking reaction after the powder is heated to a fluid state and a smooth thermoset painted surface is not obtained. Another reason is that it is substantially difficult to produce a solid thermosetting acrylic resin which can be used for a finishing powder in a form containing no volatile ingredient. Presently known polymerization processes for producing thermoplastic acrylic solid resins include bulk-polymerization, suspension-polymerization and emulsion-polymerization. However, a thermosetting acrylic solid resin which can be used as a finishing powder is difficult to produce by any of these known polymerization processes.
More specifically, when a thermosetting acrylic is used in formation of a powdery thermosetting solid coating composition, unlike the case where it is used as a molding material, the weight average molecular weight (Mw) should not exceed about 100,000 and, by correlation, the number average molecular weight (Mn) should not exceed about 30,000. Thus, unless the number average molecular weight of a thermosetting acrylic solid resin for a finishing powder is controlled so as to be less than 30,000, the thermal fluidity or flowability is so low that the resin cannot be put into practical use. In that case, such a large amount of polymerization initiator is required that when attempting production by the bulk polymerization process, it is difficult to control the heat generated by the polymerization. When attempting production by the suspension-polymerization process, since the functional groups of the monomer impart high water-solubility, it is difficult to complete the polymerization while maintaining stability of the suspension state; therefore the suspension-polymerization process cannot be adopted to any great extent. When attempting the production by the emulsion-polymerization process, in practice, the emulsifier is mixed into the painted film and a weather proof painted film cannot be obtained.
SUMMARY
It is therefore an object of the present invention to provide a process for producing thermosetting finished powders wherein a solid thermosetting acrylic resin is used.
It is another object of the present invention to provide such thermosetting finishing powders which exhibit high thermal fluidity.
It is a further object of the present invention to provide such thermosetting finishing powders which overcome the deficiencies in thermal stability, resistance to solvents and adhesion to metals exhibited by vinyl chloride type resins.
It is still another object of the present invention to provide such thermosetting finishing powders which overcome the deficiency in durability to weathering exhibited by epoxy type resins.
It is yet another object of the present invention to provide such thermosetting finishing powders which overcome the deficiencies in mechanical strength and resistance to solvents exhibited by thermoplastic acrylic resins.
It is another object of the present invention to provide solid copolymers and processes for producing the same, which solid copolymers are useful in preparing such thermosetting finishing powders.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. It has been found that the above objects can be attained by practicing the present invention.
One embodiment of the present invention includes a process for producing solid copolymers (a) having a glass transition point of from 5° to 60° C. and a number average molecular weight of from 1,500 to 30,000 by bulk-polymerizing a monomer mixture consisting of a cross-linkable monomer having the structure: ##STR2## wherein R1 is H or CH3 and R2 is an alkyl radical containing from 1 to 14 carbon atoms, in an amount at least 30% by weight based on the total monomers to be copolymerized, an ethylenic α, β unsaturated carboxylic acid monomer in an amount from 3 to 20% by weight based on the total monomers to be copolymerized and 0 to 67% by weight based on the total monomers to be copolymerized of a monomer copolymerizable with each of the above monomers, until conversion to the polymer is from 10 to 80% by weight and then adding a polymerization initiator and completing the polymerization by suspension-polymerization.
Another embodiment of the present invention includes a process for producing solid copolymers (b) having a glass transition point of from 5° to 60° C. and a number average molecular weight of from 1,500 to 30,000 by bulk-polymerizing a monomer mixture consisting of a cross-linkable monomer having the structure: ##STR3## wherein R1 is H or CH3 and R2 is an alkyl radical of containing from 1 to 14 carbon atoms, in an amount at least 30% by weight based on the total monomers to be copolymerized, a monomer having the structure: ##STR4## wherein R1 is H or CH3, in an amount from 3 to 40% by weight based on the total monomers to be copolymerized and a monomer copolymerizable with each of the above monomers in an amount of 0 to 67% by weight based on the total monomers to be copolymerized until conversion to the polymer is from 10 to 80% by weight and then adding a polymerization initiator and completing the polymerization by suspension-polymerization.
A thermosetting finishing powder is produced by mixing 40 to 5 parts by weight of an epoxy resin containing 2 or more epoxy radicals in the molecule and from 0.02 to 2.0 parts by weight of a tertiary amine having the structure: ##STR5## wherein each of R1, R2 and R3 is alkyl containing from 1 to 8 carbon atoms or phenyl, or a derivative thereof, as a curing accelerator, with 60 to 95 parts by weight of the solid copolymer (a) produced by the above described process and then crushing the mixture to a powder. Also, a thermosetting finishing powder is produced by mixing 40 to 3 parts by weight of a cross-linking compound containing 2 or more equivalents of carboxyl radicals or acid anhydrides thereof in the molecule or 40 to 3 parts by weight of a cross-linking compound containing in the molecule at least 2 nitrogen atoms having adjacent thereto at least one active hydrogen (and thus containing at least two structures having the formula: ##STR6## wherein one or both of R1 and R2 is hydrogen) with 60 to 97 parts by weight of the solid copolymer (b) produced by the respective above described process.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be explained more particularly in the following detailed description.
The monomers which have the general formula: ##STR7## wherein R1 is H or CH3 and R2 is an alkyl radical containing from 1 to 14 carbon atoms, which are used to produce solid copolymers (a) and (b) by the above-described processes of the present invention include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and tridecyl methacrylates. These monomers impart excellent thermal stabilty and weatherability to the resulting thermosetting solid coating composition and at least one is used in the present invention. When the amount of said monomer used is less than 30% by weight based on the total monomers to be copolymerized, the durability against weathering, metal adhesion and thermal stability of the obtained finish are reduced.
The ethylenic α, β unsaturated carboxylic acid monomers used in the above described process to obtain solid copolymer (a) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic anhydride. These monomers react with the epoxy resin to cause thermosetting and improve solvent resistance of the resulting thermosetting solid coating composition and at least one of the monomers is used. If the amount of said ethylenic α, β unsaturated carboxylic acid monomer used is less than 3% by weight based on the total monomers to be copolymerized, it does not measurably contribute to an improvement of solvent resistance and mechanical strength. On the other hand, if the amount exceeds 20% by weight, the thermal fluidity is reduced and no smooth painted surface is obtained. Also, in this instance, the monomer would tend to react with the epoxy resin during mixing by melt-kneading to cause undesired gelation.
The monomers having the general formula: ##STR8## wherein R1 is H or CH3, which are used in the above described process to obtain solid copolymer (b) are glycidyl acrylate and glycidyl methacrylate. These monomers react with either of the above described cross-linking compounds, e.g. when the coating composition is actually applied, and also contribute to the improvements in solvent resistance and mechanical strength of the finishing powders obtained by the present invention. If the amount of this monomer used is less than 3% by weight of the total monomers to be copolymerized, no sufficient cross-linking reaction can be expected and therefore the solvent resistance and mechanical strength of the obtained finishing powder are low. On the other hand, if the amount exceeds 40% by weight, the cross-linking reaction occurs while the heat flow is insufficient in the baking step after painting and also the smoothness of the painted surface is poor.
In the solid copolymer (a) or (b) obtained by the above described processes, it is very important for the practical use of the finishing powder to limit the ranges of the glass transition point and the number average molecular weight. If the glass transition point is below 5° C., the produced finishing powder tends to be sticky and cohere and therefore cannot be used in practice. When it exceeds 60° C., the thermal fluidity is too low for practical use. Further, if the number average molecular weight is less than 1500, the solvent resistance and mechanical strength are reduced. When it exceeds 30,000, the thermal fluidity becomes so low that a smooth painted surface is not obtained.
The monomers copolymerizable with each of the above described monomers include, for example, styrene, α-methyl styrene, vinyl toluene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, β-hydroxyethyl acrylate and β-hydroxypropyl methacrylate. However, when their amount exceeds 67% by weight, the durability against weathering, metal-adhesion and thermal stability of the product are reduced. Furthermore, the amount of these monomers must also satisfy the limiting conditions of the glass transition point and number average molecular weight of the resultant copolymers.
In the present invention, in producing solid copolymers (a) and (b), the mixture of the monomers is copolymerized at a temperature of from 80° to 150° C., preferably 100° to 130° C., by a bulk-polymerization process until conversion to the polymer has reached 10 to 80% by weight, then suspension-polymerization is carried out. If conversion to the polymer is less than 10% by weight, and if suspension-polymerization is then used, the cross-linkable monomers as described above are so highly water-soluble that they dissolve into the water layer and it is difficult to maintain a favorable suspension state and a solid copolymer suitable for use for the finishing powder of the present invention is not obtained. On the other hand, if conversion to the polymer by bulk-polymerization is above 80% by weight it is difficult to maintain the number average molecular weight below 30,000 and the thermal fluidity of the copolymer is lowered. The temperature adopted for the suspension polymerization will vary depending on the polymerization initiator used but in general will range between 60° and 100° C.
In the suspension-polymerization step of the present invention, in either of the above described processes for producing copolymers (a) and (b), the polymerization initiators used are conventional radical polymerization initiators, for example, organic peroxides represented by benzoyl peroxide and lauroyl peroxide and azobisnitriles such as azobisisobutylonitrile. The polymerization initiator is used in an amount of from 0.5 to 5.0% by weight of the total monomers to be copolymerized. However, it is possible to add a portion of the polymerization initiator in a range allowing for control of the polymerization heat in the bulk-polymerization step. Use of the polymerization initiator is effective for adjusting the number average molecular weight of the polymer obtained after completion of the suspension polymerization step of the process of the invention. In either of the bulk-polymerization and/or suspension-polymerization steps, the number average molecular weight can be further adjusted, if necessary, between 1,500 to 30,000 by using less than 5% by weight of a chain transfer agent such as a mercaptan, for example, primary or tertiary dodecylmercaptan, a disulfide, for example, diisopropylxanthogen disulfide, a diazothioether or a halide.
In the suspension polymerization step by either process for obtaining copolymer (a) and (b), the dispersing agents used are high molecular weight organic substances such as gelatin, tragacanth, starch, methyl cellulose and carboxymethyl cellulose and synthetic high molecular weight substances such as polyvinyl alcohols, partially saponified polyvinyl alcohols, polyacrylates and polyacrylamides, inorganic salts such as BaSO4, CaSO4, CaCO3, MgCO3 and Ca3 (PO4)2, inorganic high molecular weight substances such as talc, bentonite, silicic acid, diatomaceous earth and clay and metals and metal oxides, that are known as dispersing agents. in suspension-polymerization. Further, such known salts as NaCl. KCl and Na2 SO4 and surface active agents of the anionic, cationic and nonionic types may be simultaneously used as dispersing assistants.
In the present invention, a two-stage polymerization by bulk-polymerization and suspension-polymerization is used, so that the greater part of the above described cross-linkable monomers which are highly water-soluble may be introduced into the polymer chains during the bulk-polymerization step so as to be insoluble in water and therefore, in the suspension-polymerization stage, it is possible to maintain a favorable suspension state, a favorable pearly polymer which can be used substantially as a thermosetting finishing powder is obtained and it is also possible to adjust the number average molecular weight of the polymer within a range of 1,500 to 30,000.
By each of the above described processes for obtaining copolymers (a) and (b), a solid copolymer according to the present invention is obtained. A thermosetting finishing powder is produced by dehydrating the copolymer, then drying it with a fluid layer dryer, air current dryer or hot-air dryer and then mixing it with such cross-linking agent to be used in the present invention as will be seen in the following.
Typical epoxy resins which have two or more epoxy radicals in the molecule and which are cross-linking agents to be mixed with the solid copolymer (a) obtained by the above described process are: polyvalent epoxy compounds obtained by the condensation of bisphenol A and epichlorohydrin or β-methylepichlorohydrin; polyvalent epoxy compounds obtained by the condensation of a novolak or resol and epichlorohydrin; diepoxy compounds having a polyether in the skeleton; and alicyclic epoxy compounds.
When the sum of the solid copolymer (a) and the epoxy resin cross-linking agent is considered as 100%, if the amount of the epoxy resin is less than 5%, the solvent resistance and mechanical strength of the obtained thermosetting finishing powder become poor and, if it exceeds 40% by weight, the durability against weathering is unsatisfactory. In this embodiment it is preferable to add a curing accelerator to the mixture. The above described tertiary amine curing accelerators and derivatives thereof include, for example, trimethylamine, triethylamine, triisopropylamine, dimethylbenzylamine, triethylammonium chloride, triisopropylammonium chloride, dimethylbenzylammonium chloride, triethylamine sulfonate and boron trifluoride-triethylamine complex compound. They are used preferably in an amount from 0.02 to 2.0 parts by weight per 100 parts by weight of the resin solid. The use of this amine component promotes the thermosetting reaction between the carboxylic acid of the solid copolymer (a) and the epoxy group at the time of actual application. If the amount of amine component is less than 0.02 part by weight, the solvent resistance of the resulting thermosetting coating composition is insufficient and if the amount exceeds 2.0 parts by weight, the viscosity increases extremely at the time of the mixing operation so that it is difficult to obtain a powdery composition and thermal stability is lowered.
The solid copolymer (a) and the epoxy resin are put into a heatable mixing machine such as, for example, an extruder, a co-kneader or a Henschel type mixer, and melted and mixed at a temperature in the range of 120° to 200° C. In this operation the solid copolymer (a) and the epoxy resin may be mixed and melted simultaneously, or it is possible to premelt one of the two components and then mix the melt with the second component. In either method, the obtained melt is cooled, if necessary, to a temperature not exceeding 150° C. and then the curing accelerator is added and mixed therewith. When the mixture consistency becomes uniform, it is cooled and crushed.
When the temperature in the above initial mixing is below 120° C., it is difficult to melt and mix the components uniformly. When the temperature exceeds 200° C., the copolymer (a) tends to be depolymerized. Further, when the mixing temperature of the curing accelerator exceeds 150° C., a cross-linking reaction tends to occur during the mixing and the thermal fluidity of the finishing powder is reduced. Therefore, it is necessary to keep this mixing temperature at 150° C. or below.
The cross-linking compounds which contain two or more equivalents of a carboxyl radical or acid anhydride thereof in the molecule and which are mixed with solid copolymer (b), include such polyvalent carboxylic acid compounds as phthalic anhydride, isophthalic acid, adipic acid, succinic acid, sebacic acid, citric acid, itaconic acid, aconitic acid, maleic anhydride, fumaric acid, trimellitic anhydride, hexahydrophthalic acid, tetrahydrophthalic anhydride, dodecenyl succinic anhydride, pimelic acid and pyromellitic anhydride, polyester resins having two or more carboxyl radicals in the molecule which are obtained by esterification of these polyvalent carboxylic acid compounds with polyhydric alcohols, and solid copolymers (a) wherein two or more ethylenic α, βunsaturated carboxylic acid monomers are copolymerized in the molecule.
The cross-linking compounds which contain two or more nitrogen atoms having one or two active hydrogen atoms adjacent thereto in the molecule include cyclohexylaminopropylamine, methaphenylene diamine, p,p'-diaminodiphenyl methane, p,p'-diaminodiphenyl sulfone, dicyandiamide, polyamide resins having in the molecule at least two amide groups and epoxy-amine adducts containing in the molecule at least two nitrogen atoms adjacent to an active hydrogen atom, which are obtained by reacting an amine with an epoxy resin.
Both of the above types of cross-linking compounds exhibit compatability with the above solid copolymer (b) when rendered molten by heating but they do not react with the copolymer to cause cross-linking before they are rendered molten. It is also necessary that they do not exhibit viscosity or stickiness when admixed with the solid copolymer (b). An appropriate selection of a desired cross-linking compound having these properties is made dependent upon the composition, glass transition point and number average molecular weight of the solid copolymer (b).
When the amount of the cross-linking agent is less than 3% by weight of the total weight of cross-linking agent and copolymer (b), no sufficient thermosetting occurs and therefore the solvent resistance and mechanical strength are low. When the amount exceeds 40% by weight, the durability against weathering is reduced, and the thermal fluidity is greatly reduced in some cases.
The solid copolymer (b) and the cross-linking compound are mixed together and then crushed or ground at room temperature or below, e.g. at 0° to 30° C., to a powder, e.g. of 40 to 300 mesh. In cases when the cross-linking compound is a liquid or viscous mass rather than a solid, the solid copolymer (b) is preferably rendered molten, e.g. by means of a kneader capable of high agitation and heating, the cross-linking compound is incorporated in the melt and the mixture is then cooled to room temperature or below, e.g. to 20° to 30° C. and crushed or ground to a powder, e.g. of 40 to 300 mesh.
The thermosetting finishing powders of the present invention when applied as a coating may also include inorganic fillers such as titanium oxide, iron oxide, silica, calcium carbonate or barium sulfate, organic pigments such as carbon black, phthalocyanine blue or Sincasia red, modified cellulose such as cellulose acetate butyrate, methoxycellulose or ethoxycellulose, a plasticizer such as dibutyl phthalate, dioctyl phthalate or epoxidized oil or other additives such as silicone or wax. They are mixed with the powders by a dry-blending process, semi-dry-blending process or melt-blending process, and are then crushed to a powder. In the embodiment of the present invention wherein the amine curing accelerator is used, the above-additives are preferably incorporated prior to mixing of the curing accelerator because the time required for mixing is substantially lengthened if the curing accelerator is added first. Then the thermosetting finishing powder produced by the above described method is applied as a coating on a base material such as a metal and is then baked for from 5 to 60 minutes within a dryer at 160° to 220° C. to obtain a thermoset painted film which is high in thermal fluidity during baking and is excellent in thermal stability, solvent resistance, metal-adhesion, mechanical strength and durability against weathering.
The present invention will be more fully understood with reference to the following examples.
EXAMPLE 1
Examples 1 and 2 show a process for using a solid copolymer obtained by copolymerizing an ethylenic α, β unsaturated carboxylic acid monomer in producing a thermosetting finishing powder.
Raw materials used in a bulk-polymerization according to each of runs (A) to (E) shown in Table I were put into an autoclave reactor having a capacity of 4 liters and equipped with an agitator, reflux condenser, thermometer and nitrogen inlet. The air in the reactor was replaced with nitrogen. The mixture of raw materials described in the table was heated and the temperature was kept at 110° to 120° C. with agitation. Each bulk-polymerization was carried out to obtain conversions to the polymer and for the polymerization times shown in the table. When the bulk-polymerization was completed, the reaction product was cooled and was agitated with the addition of polymerization initiator, dispersing agent and ion-exchanged water as indicated in the table. The polyvinyl alcohol used had a saponification degree of 80%. While the reaction product was kept suspended, suspension-polymerization was carried out at the temperatures and times shown in Table I. The obtained product was washed with water and dried with a vacuum dryer to obtain a pearly copolymer having a grain diameter of 50 to 150 meshes per inch. The glass transition points and number average molecular weights of the respective obtained copolymers are also shown in the table.
                                  TABLE I                                 
__________________________________________________________________________
                       A   B   C   D   E                                  
__________________________________________________________________________
        Ethyl acrylate     450                                            
        n-butyl acrylate                                                  
                       224             100                                
        2-ethylhexyl acrylate  150                                        
        Methyl methacrylate        550                                    
        Ethyl methacrylate     180                                        
        n-butyl methacrylate                                              
                           100         450                                
        Isobutyl methacrylate                                             
                       676                                                
Raw materials                                                             
        Lauryl methacrylate    150 250                                    
at the time                                                               
        Styrene            350                                            
of the bulk-                                                              
        α-methylstyrene  450                                        
polymerization                                                            
        Vinyl toluene                  400                                
(in parts by                                                              
        Acrylonitrile              50                                     
weight) Vinyl acetate              100                                    
        Acrylic acid           70                                         
        Methacrylic acid                                                  
                       100 100                                            
        Itaconic acid              50                                     
        Maleic anhydride               50                                 
        n-butylmercaptan   5                                              
        n-dodecylmercaptan             10                                 
        Tertiary dodecylmercaptan                                         
                               10                                         
        Diisopropylxanthogendisulfide                                     
                                   10                                     
__________________________________________________________________________
Period of time in the bulk-polymerization                                 
  (in hours)           2   4   5   4   4                                  
__________________________________________________________________________
Conversion to polymer when bulk-                                          
polymerization was stopped (in % by weight)                               
                       21.7                                               
                           40.6                                           
                               45.2                                       
                                   36.6                                   
                                       34.7                               
__________________________________________________________________________
Raw materials                                                             
        Azobisisobutylonitrile                                            
                           30                                             
at the time                                                               
        Benzoyl peroxide                                                  
                       35              40                                 
of the  Lauroyl peroxide       40                                         
suspension-                                                               
        Parachlorobenzoyl peroxide 40                                     
polymerization                                                            
        Polyvinyl alcohol          20                                     
(in parts by                                                              
        Tricalcium phosphate                                              
                           10  10      20                                 
weight) Ion-exchanged water                                               
                       3000                                               
                           3000                                           
                               3000                                       
                                   3000                                   
                                       3000                               
__________________________________________________________________________
Temperature in the suspension                                             
polymerization (in ° C)                                            
                       90  80  90  90  90                                 
__________________________________________________________________________
Period of time in the suspension-                                         
polymerization (in hours)                                                 
                       6   7   5   5   6                                  
__________________________________________________________________________
Glass transition point of the solid                                       
copolymer (in ° C)                                                 
                       25  28  33  33  38                                 
__________________________________________________________________________
Number average molecular weight                                           
of the solid copolymer 21000                                              
                           6800                                           
                               10200                                      
                                   6300                                   
                                       5900                               
__________________________________________________________________________
EXAMPLE 2
Using the solid copolymers A-E obtained in Example 1, thermosetting finishing powders were produced by the following process.
The solid copolymer and titanium oxide were put into a Henschel type mixer, and were melted and blended according to the conditions shown in Table 2. Then the epoxy resin shown in the table was mixed therewith. After the melted mixture was cooled to a temperature of from 110° to 120° C., the curing accelerator shown in the table was mixed therewith. Then the melted mixture was immediately cooled and was crushed with a crusher. The powder passing through a sieve of 150 meshes per inch was collected to produce a thermosetting finishing powder shown in each of Runs 1-7 in the table. All of the numerical values in the table with the exception of the blending temperatures indicate parts by weight.
                                  TABLE II                                
__________________________________________________________________________
Run No.        1    2   3  4   5   6    7                                 
__________________________________________________________________________
Titanium oxide 50  50  50  50  50  50  50                                 
Solid copolymer (A)                                                       
               80      85                                                 
Solid copolymer (B)                                                       
                   80                                                     
Solid copolymer (C)        85                                             
Solid copolymer (D)            75  85                                     
Solid copolymer (E)                    95                                 
__________________________________________________________________________
Blending temperature (° C)                                         
               180 170 180 160 160 160 160                                
__________________________________________________________________________
Epikote 820 *1 20                      10                                 
Epikote 834 *1         15                                                 
Epikote 1001               25                                             
DEN 431 *2         20                                                     
Unox T-206 *3          15                                                 
Epichlon 800 *4                    15                                     
BF.sub.3 dimethylbenzylamine                                              
complex compound                                                          
               1.5                                                        
Triisopropylamine  0.2     1.0                                            
Triethylammonium chloride                                                 
                       1.0     1.5     2.0                                
Triethylamine paratoluene                                                 
 sulfonate                         1.5                                    
__________________________________________________________________________
 In the above table:                                                      
 (1) *1 is a trade name of an epoxy resin produced by Shell Chemical      
 Company, Britain.                                                        
 (2) *2 is a trade name of an epoxy resin produced by Dow Chemical Company
 U.S.A.                                                                   
 (3) *3 is a trade name of an epoxy resin produced by Union Carbide       
 Company, U.S.A.                                                          
 (4) *4 is a trade name of an epoxy resin produced by Dainippon Ink       
 Chemical Company, Japan.                                                 
 The characteristic evaluations of the thermosetting finishing powders    
 obtained by the present invention and shown in Runs 1-7 in the above tabl
 are shown in the following Table 3.
On steel plates of a thickness of 0.8 mm. treated with zinc phosphate each of the thermosetting finishing powders 1 to 7 shown in the above table and such controls as an epoxy resin finishing powder, vinyl chloride resin finishing powder and thermoplastic acrylic resin finishing powder were painted with an electrostatic powder coating machine and then baked for 20 minutes in a hot-air dryer adjusted to a temperature of 200° C. The obtained respective test plates were evaluated respective to the characteristics of each painted film on the test plates. The results are collectively shown in the table. Tested powders 1-7 represent the present invention and the remaining powders are prior art powders for control and comparison purposes.
                                  TABLE III                               
__________________________________________________________________________
Film characteristcs                                                       
           Thermal                                                        
                  Solvent Resistance.sub.5                                
                             Thermal stability.sub.6                      
Tested                                                                    
     Thickness                                                            
           fluidity.sub.4                                                 
                  (Methyl ethyl                                           
                             (Yellowing                                   
films                                                                     
     (in μ)                                                            
           (Smoothness)                                                   
                  ketone)    when rebaked)                                
__________________________________________________________________________
1    89    Good   Unchanged  None                                         
2    85    Good   Unchanged  None                                         
3    83    Good   Unchanged  None                                         
4    80    Good   Unchanged  None                                         
5    84    Good   Unchanged  Slight                                       
                             Yellowing                                    
6    86    Good   Unchanged  Slight                                       
                             Yellowing                                    
7    82    Good   Unchanged  None                                         
Epoxy                                                                     
     82    Good   Unchanged  Quite                                        
powder.sub.1                 Yellow                                       
Vinyl                                                                     
chloride                                                                  
     130   Good   Paint film Very                                         
powder.sub.2      dissolved  Yellow                                       
Thermo-                                                                   
plastic                                                                   
     84    Good   Paint film None                                         
acrylic           dissolved                                               
powder.sub.3                                                              
__________________________________________________________________________
Film characteristcs                                                       
Mechanical  Metal  Weathering durability.sub.9 :                          
            strength.sub.7 :                                              
                   adhesion.sub.8 :                                       
                                   Weather-O-Meter irradiation            
Tested                                                                    
     Du pont                                                              
            Cross-cut                                                     
                   % Gloss Degree of                                      
Films                                                                     
     impact test                                                          
            test   retention                                              
                           Yellowing                                      
__________________________________________________________________________
1    No cracks                                                            
            No peeling                                                    
                   90      None                                           
2    No cracks                                                            
            No peeling                                                    
                   81      None                                           
3    No cracks                                                            
            No peeling                                                    
                   85      None                                           
4    Slight No peeling                                                    
                   84      None                                           
     cracking                                                             
5    No cracks                                                            
            No peeling                                                    
                   82      None                                           
6    No cracks                                                            
            No peeling                                                    
                   88      None                                           
7    No cracks                                                            
            No peeling                                                    
                   84      None                                           
Epoxy                                                                     
     No cracks                                                            
            No peeling                                                    
                   46      Substantial                                    
powder.sub.1               Yellowing                                      
Vinyl       Peeling                                                       
chlorde                                                                   
     No cracks                                                            
            over entire                                                   
                   76      None                                           
powder.sub.2                                                              
            surface                                                       
Thermo-                                                                   
     Substantial                                                          
            Partially                                                     
plastic                                                                   
     cracking                                                             
            peeled 90      None                                           
acrylic                                                                   
powder.sub.3                                                              
__________________________________________________________________________
 In the above table:                                                      
 .sub.1 The epoxy resin finishing powder was prepared by mixing           
 dicyandiamide in an epoxy resin (Epikote 1004 produced by Shell Chemical 
 Company).                                                                
 .sub.2 The vinyl chloride finishing powder was prepared by mixing dioctyl
 phthalate in vinyl chloride resin.                                       
 .sub.3 The thermoplastic acrylic resin finishing powder was prepared by  
 using a thermoplastic acrylic resin consisting of methyl methacrylate and
 n-butyl acrylate and having a number average molecular weight of 32,000  
 and a glass transition point of 52° C.                            
 .sub.4 The thermal fluidity values are the result of judging the         
 smoothness of the painted surface of the test plate with the naked eye.  
 .sub.5 The solvent resistance values are the result of judging the degree
 of softening and the surface state after dipping the test plate in methyl
 ethyl ketone at 30° C. for 1 hours.                               
 .sub..sub.6 The thermal stability values are the result of judging the   
 degree of yellowing after heating the test plate at 200° C. for 30
 minutes.                                                                 
 .sub..sub.7 The mechanical strength values are the result of judging the 
 cracking of the painted film after dropping a load of 500 grams onto the 
 test plate from a height of 30 cm. by using a striking core of a diameter
 of 1/2 inch with a Du Pont impact tester.                                
 .sub.8 The metal-adhesion values are the result of making 11 cuts at     
 intervals of 1 mm. in each of the longitudinal and lateral directions on 
 the painted surface of the test plate with a microknife and pasting an   
 adhesive tape on the surface and judging whether or not the tape peeled  
 off when it was attempted to peel it off.                                
 .sub.9 The weathering durability values are the result of keeping the tes
 plate in a Sunshine Weather-O-Meter for 300 hours and judging the gloss  
 retention rate and the degree of discoloration.
EXAMPLE 3
Examples 3 and 4 show a process for using a solid copolymer obtained by copolymerizing a glycidyl acrylate or glycidyl methacrylate monomer in producing a thermosetting finishing powder.
The raw materials used for the bulk-polymerization step, shown in the following Table IV under Runs F to I, were put into an autoclave reactor having a capacity of 4 liters and provided with an agitator, reflux condenser, thermometer and nitrogen inlet. The air in the reactor was replaced with nitrogen. The mixture was heated and the temperature was kept at 110° to 120° C. with agitation. Each bulk-polymerization step was continued until the conversion to the polymer shown in the table was reached.
As soon as the bulk-polymerization step was completed, the reaction product was cooled and then agitated with addition of the amounts of polymerization initiator, dispersing agent and ion exchanged water shown in the table. While the product was kept suspended, suspension-polymerization was carried out under the conditions shown in the table. The obtained product was washed with water and then dried with a vacuum dryer to obtain a pearly copolymer having a grain diameter of 50 to 150 meshes per inch. The glass transition points and number average molecular weights of the respective obtained polymers are also shown in the table. The polyvinyl alcohol used had a saponification degree of 80%.
                                  TABLE IV                                
__________________________________________________________________________
         Run No.            F   G   H   I                                 
__________________________________________________________________________
         Ethyl acrylate         200                                       
         n-butyl acrylate               100                               
         Methyl methacrylate                                              
                            450                                           
         Ethyl methacrylate         600                                   
         n-butyl methacrylate                                             
                            350                                           
         Isobutyl methacrylate          300                               
         2-ethylhexyl methacrylate                                        
                                150                                       
         Tridecyl methacrylate          100                               
Raw materials                                                             
         β hydroxyethyl methacrylate                                 
                            20                                            
at the time                                                               
         Glycidyl methacrylate                                            
                            180         100                               
of the bulk-                                                              
         Glycidyl acrylate      150 200                                   
polymerization (in                                                        
         Styrene                        300                               
parts by weight)                                                          
         Vinyl toluene          500                                       
         Methacrylonitrile              100                               
         Vinyl propionate           200                                   
         Diisopropylxanthogen disulfide                                   
                            5                                             
         Tertiary dodecyl mercaptane                                      
                                5                                         
         Cumene hydroperoxide       3                                     
         Diazo thioether                5                                 
__________________________________________________________________________
Period of time of the bulk-polymerization (in hours)                      
                            6   5   2   2                                 
__________________________________________________________________________
Conversion to polymer when the bulk-polymerization                        
was finished (in % by weight)                                             
                            28.0                                          
                                34.0                                      
                                    40.2                                  
                                        15.5                              
__________________________________________________________________________
         Azobisisobutylonitrile                                           
                            30                                            
         Benzoyl peroxide       25                                        
Raw materials                                                             
          Methyl ethyl ketone peroxide                                    
                                    30                                    
at the time of                                                            
         Tertiary butyl perbenzoate     40                                
the suspension-                                                           
         Polyvinyl alcohol  30                                            
polymerization (in                                                        
         Tricalcium phosphate   30      50                                
parts by weight)                                                          
         Dibasic calcium phosphate  45                                    
         Ion-exchange water 3000                                          
                                3000                                      
                                    3000                                  
                                        3000                              
__________________________________________________________________________
Temperature in the suspension-polymerization (in ° C)              
                            80  90  75  100                               
__________________________________________________________________________
Period of time of the suspension-polymerization                           
(in hours)                  6   6   10  11                                
Glass transition point of the solid copolymer (in 20  C)                  
                            24  28  34  39                                
Number average molecular weight of the solid copolymer                    
                            7800                                          
                                11000                                     
                                    15200                                 
                                        7100                              
__________________________________________________________________________
EXAMPLE 4
The solid copolymers F-I obtained in Example 3 were made into thermosetting finishing powders by the following method.
The solid copolymer and titanium oxide were put into a Henschel type mixer and were melted and mixed according to Run Nos. 8-13 shown in the following Table V. Then a cross-linking agent as shown in the table was mixed into the melted mixture. When a curing accelerator was added, it was mixed after the melted mixture was cooled to a temperature in the range of 100° to 120° C.
The melted mixture was then immediately cooled and crushed with a crusher. The powder passing through a sieve of 150 meshes per inch was collected to produce the thermosetting finishing powders. All the numerical values in the table with the exception of the blending temperature indicate parts by weight.
              TABLE V                                                     
______________________________________                                    
Run No.        8      9      10   11   12   13                            
______________________________________                                    
Titanium oxide 50     50     50   50   50   50                            
Solid copolymer (F)                                                       
               90                      60                                 
Solid copolymer (G)   92                                                  
Solid copolymer (H)          90             80                            
Solid copolymer (I)               90                                      
______________________________________                                    
Blending temperature                                                      
(in ° C)                                                           
               160    150    150  160  160  160                           
______________________________________                                    
Hexahydrophthalic                                                         
anhydride                    10                                           
Trimellitic anhydride                                                     
               10                                                         
P,P'-diaminodiphenyl-                                                     
methane                           15                                      
Dicyandiamide         18                                                  
Ethyleneglycol diadipate                    20                            
Solid copolymer (A)                    40                                 
Dibutyl tin laurate          0.5                                          
Monoethylamine BF.sub.3                                                   
complex                           0.5                                     
Dimethyl benzylamine                        1.0                           
Salicylic acid                    0.1                                     
______________________________________
The characteristic evaluation of the thermosetting finishing powders obtained by the present invention and described in Runs 8-13 of Example 4 are shown in the following Table VI. The thermosetting finishing powders 8-13 and an epoxy resin finishing powder, vinyl chloride resin finishing powder and thermoplastic acryl resin finishing powder for comparison purposes were painted with an electrostatic powder painting apparatus onto steel plates, having a thickness of 0.8 mm. and treated with zinc phosphate, and were further baked for 20 minutes with a hot-air dryer adjusted to a temperature of 200° C. to obtain the respective test plates. The results are collectively shown in the table. The finishing powders used for comparison and the testing methods were the same as used in Example 2 and as shown in Table III.
                                  TABLE VI                                
__________________________________________________________________________
Film characteristics                                                      
           Thermal                                                        
                  Solvent Resistance                                      
                             Thermal stability                            
Tested                                                                    
     Thickness                                                            
           fluidity                                                       
                  (Methyl ethyl                                           
                             (Yellowing                                   
films                                                                     
     (in/μ)                                                            
           (Smoothness                                                    
                  ketone)    when rebaked)                                
__________________________________________________________________________
 8   80    Good   Unchanged  None                                         
 9   85    Good   Unchanged  Slight                                       
                             Yellowing                                    
10   82    Good   Unchanged  None                                         
11   88    Good   Unchanged  Slight                                       
                             Yellowing                                    
12   83    Good   Unchanged  None                                         
13   90    Good   Unchanged  None                                         
Epoxy                                                                     
powder                                                                    
     82    Good   Unchanged  Slight                                       
                             Yellowing                                    
Vinyl             Paint film Very                                         
chloride                                                                  
     130   Good   dissolved  Yellow                                       
powder                                                                    
Thermo-           Paint film                                              
plastic                                                                   
     84    Good   dissolved  None                                         
acrylic                                                                   
powder                                                                    
__________________________________________________________________________
Film characteristics                                                      
Mechanical  Metal  Weathering durability:                                 
strength    adhesion:                                                     
                   Weather-O-Meter irradiation                            
__________________________________________________________________________
Tested                                                                    
     Du Pont                                                              
            Cross-cut                                                     
                   % Gloss Degree of                                      
films                                                                     
     impact test                                                          
            test   retention                                              
                           Yellowing                                      
__________________________________________________________________________
 8   Slight No peeling                                                    
                   92      None                                           
     cracking                                                             
 9   No cracks                                                            
            No peeling                                                    
                   81      None                                           
10   No cracks                                                            
            No peeling                                                    
                   94      None                                           
11   No cracks                                                            
            No peeling                                                    
                   86      Slight                                         
                           Yellowing                                      
12   No cracks                                                            
            No peeling                                                    
                   91      None                                           
13   No cracks                                                            
            No peeling                                                    
                   88      None                                           
Epoxy                      Substantial                                    
powder                                                                    
     No cracks                                                            
            No peeling                                                    
                   46      Yellowing                                      
Vinyl       Peeling                                                       
chloride                                                                  
     No cracks                                                            
            over entire                                                   
                   76      None                                           
powder      surface                                                       
Thermo-                                                                   
plastic                                                                   
     Substantial                                                          
            Partially                                                     
                   90      None                                           
acrylic                                                                   
     cracking                                                             
            peeled                                                        
powder                                                                    
__________________________________________________________________________

Claims (7)

What is claimed is:
1. A process for producing a solid copolymer having a glass transition point of from 5° to 60° C and a number average molecular weight of from 1,500 to 30,000 which comprises copolymerizing a mixture of:
A. at least 30% by weight of total monomers of a monomer having the formula: ##STR9## wherein R1 is selected from the group consisting of H and CH3 and R2 is an alkyl radical containing from 1 to 14 carbon atoms;
B. a member selected from the group consisting of
1. from 3 to 20% by weight of total monomers of a monomer selected from the group consisting of ethylenic α,β unsaturated mono and dicarboxylic acids and anhydrides thereof,
2. from 3 to 40% by weight of total monomers of a monomer selected from glycidyl acrylate and glycidyl methacrylate; and
c. from 0 to 67% by weight of total monomers of an ethylenically monounsaturated monomer copolymerizable with said monomers (A) and (B),
the mixture being first bulk-polymerized until conversion to the copolymer is from 10% to 80% by weight and polymerization then being completed by suspension-polymerization in the presence of an effective amount of a polymerization initiator.
2. The process according to claim 1 wherein said member (B) is a monomer selected from the group consisting of ethylenic α,β unsaturated mono and dicarboxylic acids and anhydrides thereof.
3. The process according to claim 1 wherein said member (B) is a monomer selected from the group consisting of glycidyl acrylate and glycidyl methacrylate.
4. The process according to claim 1 wherein said monomer (C) is selected from the group consisting of styrene, α-methyl styrene, vinyl toluene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, β-hydroxyethyl acrylate, β-hydroxypropyl methacrylate and mixtures thereof.
5. A thermosetting solid coating composition which comprises a powdery mixture prepared by mixing together and then crushing or grinding at a temperature of 0° to 30° C. to a powder:
a. 60 to 97% by weight of total mixture of a solid copolymer having a glass transition point of from 5° to 60° C. and a number average molecular weight of from 1,500 to 30,000 which comprises the copolymer of:
A. at least 30% by weight of total monomers of a monomer having the formula: ##STR10## wherein R1 is selected from the group consisting of H and CH3 and R2 is an alkyl radical containing from 1 to 14 carbon atoms;
B. from 3 to 40% by weight of total monomers of a monomer selected from glycidyl acrylate and glycidyl methacrylate; and
C. from 0 to 67% by weight of total monomers of an ethylenically monounsaturated monomer copolymerizable with said monomers (A) and (B), said solid copolymer being obtained by first bulk polymerizing said monomers until conversion to the copolymer is from 10% to 80% by weight and then completing polymerization by suspension-polymerization in the presence of an effective amount of a polymerization initiator; and
b. 40 to 3% by weight of total mixture of a cross-linking compound consisting of a compound containing in the molecule at least two radicals selected from the group consisting of carboxyl radicals and carboxylic acid anhydride radicals, said cross-linking compound being compatible with said solid copolymer when rendered molten by heating but not reacting with said solid copolymer to cause cross-linking before both said solid copolymer and said cross-linking agent are rendered molten,
said powdery mixture being free of stickiness, high in thermal fluidity during baking when applied as a coating to a base material, and high in thermal stability, resistance to solvents, adhesion, mechanical strength and durability against weathering when it has been thermoset.
6. A thermosetting solid coating composition which comprises a powdery mixture prepared by mixing together and then crushing or grinding at a temperature of 0° to 30° C. to a powder:
a. 60 to 97% by weight of total mixture of a solid copolymer having a glass transition point of from 5° to 60° C. and a number average molecular weight of from 1,500 to 30,000 which comprises the copolymer of:
A. at least 30% by weight of total monomers of a monomer having the formula: ##STR11## wherein R1 is selected from the group consisting of H and CH3 and R2 is an alkyl radical containing from 1 to 14 carbon atoms;
B. from 3 to 40% by weight of total monomers of a monomer selected from glycidyl acrylate and glycidyl methacrylate; and
C. from 0 to 67% by weight of total monomers of an ethylenically monounsaturated monomer copolymerizable with said monomers (A) and (B), said solid copolymer being obtained by first bulk polymerizing said monomers until conversion to the copolymer is from 10% to 80% by weight and then completing polymerization by suspension-polymerization in the presence of an effective amount of a polymerization initiator; and
b. 40 to 3% by weight of total mixture of a cross-linking compound consisting of a compound containing in the molecule at least two nitrogen atoms each having adjacent thereto at least one active hydrogen atom, said cross-linking compound being compatible with said solid copolymer when rendered molten by heating but not reacting with said solid copolymer to cause cross-linking before both said solid copolymer and said cross-linking agent are rendered molten,
said powdery mixture being free of stickiness, high in thermal fluidity during baking when applied as a coating to a base material, and high in thermal stability, resistance to solvents, adhesion, mechanical strength and durability against weathering when it has been thermoset.
US05/426,954 1969-11-27 1973-12-13 Process for producing thermosetting finishing powders Expired - Lifetime US4042645A (en)

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Cited By (26)

* Cited by examiner, † Cited by third party
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US4097350A (en) * 1974-03-22 1978-06-27 National Starch And Chemical Corporation Actinic radiation curable compositions
US4225651A (en) * 1977-05-10 1980-09-30 Rohm And Haas Company Curing membrane for concrete and the like
US4340483A (en) * 1977-01-19 1982-07-20 Ceskoslovenska Akademie Ved Polar polymeric sorbent based on glycidyl esters for gas and liquid chromatography
US4346144A (en) * 1980-07-21 1982-08-24 E. I. Du Pont De Nemours And Company Powder coating composition for automotive topcoat
US4734475A (en) * 1986-12-15 1988-03-29 Ciba-Geigy Corporation Wettable surface modified contact lens fabricated from an oxirane containing hydrophobic polymer
US4806600A (en) * 1986-04-15 1989-02-21 Mitsui Toatsu Chemicals, Incorporated Methyl methacrylate syrup composition
US4816500A (en) * 1985-11-25 1989-03-28 E. I. Du Pont De Nemours And Company Two component coating composition of an anhydride containing polymer and a glycidyl component
US4879364A (en) * 1986-10-20 1989-11-07 The B.F. Goodrich Company Film of carboxylated acrylate latex, and article made therefrom
US4880673A (en) * 1986-03-27 1989-11-14 Bayer Aktiengesellschaft Acrylate binder and its use for dressing leather
US4975484A (en) * 1985-05-10 1990-12-04 E. I. Du Pont De Nemours And Company Acrylic copolymer composition and adhesive coatings therefrom
US4980410A (en) * 1985-05-10 1990-12-25 E. I. Du Pont De Nemours And Company Acrylic copolymer composition and adhesive coatings therefrom
US5037700A (en) * 1981-01-19 1991-08-06 National Starch And Chemical Investment Holding Corporation Flexible laminates
US5116892A (en) * 1991-07-22 1992-05-26 Eastman Kodak Company Thermosetting powder coating compositions
US5322878A (en) * 1987-10-28 1994-06-21 Belland Ag Carboxylated molding copolymers
US5356988A (en) * 1991-07-17 1994-10-18 Cargill, Incorporated Acrylic polymer aqueous dispersion made through a micro dispersion
US5407707A (en) * 1993-11-01 1995-04-18 Ppg Industries, Inc. Powder coating composition based on epoxy containing polymers and polyacid curing agents
EP0776949A2 (en) 1995-12-01 1997-06-04 Ems-Inventa Ag Heat-curable powder coating
US5703177A (en) * 1994-12-16 1997-12-30 Ems-Inventa Ag Partially crystalline block copolyester-polyamides
US5844048A (en) * 1995-11-29 1998-12-01 Ems-Inventa Ag Thermosetting powder-type coating compositions
US5969058A (en) * 1997-12-23 1999-10-19 Ppg Industries Ohio, Inc. Color-plus-clear composite coating composition containing tin catalysts
US6013733A (en) * 1996-02-16 2000-01-11 Ppg Industries Ohio, Inc. Coating of film-forming resin and functional flow control copolymer
US6077608A (en) * 1996-09-19 2000-06-20 Ppg Industries Ohio, Inc. Multilayered coating with powder clear coating and substrates therewith and method
US6251999B1 (en) 1997-12-23 2001-06-26 Ppg Industries Ohio, Inc. Tin carboxylate catalysts for epoxy-acid coating compositions
US6599987B1 (en) 2000-09-26 2003-07-29 The University Of Akron Water soluble, curable copolymers, methods of preparation and uses thereof
US20040265494A1 (en) * 2003-06-25 2004-12-30 Szuping Lu Glycidyl (meth)acrylate powder coating compositions containing caprolactone-derived side chains
US20090227708A1 (en) * 2008-03-04 2009-09-10 Daly Andrew T Epoxy functional acrylic coating powders and powder coatings therefrom having improved filiform corrosion resistance

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097350A (en) * 1974-03-22 1978-06-27 National Starch And Chemical Corporation Actinic radiation curable compositions
US4340483A (en) * 1977-01-19 1982-07-20 Ceskoslovenska Akademie Ved Polar polymeric sorbent based on glycidyl esters for gas and liquid chromatography
US4225651A (en) * 1977-05-10 1980-09-30 Rohm And Haas Company Curing membrane for concrete and the like
US4346144A (en) * 1980-07-21 1982-08-24 E. I. Du Pont De Nemours And Company Powder coating composition for automotive topcoat
US5037700A (en) * 1981-01-19 1991-08-06 National Starch And Chemical Investment Holding Corporation Flexible laminates
US4975484A (en) * 1985-05-10 1990-12-04 E. I. Du Pont De Nemours And Company Acrylic copolymer composition and adhesive coatings therefrom
US4980410A (en) * 1985-05-10 1990-12-25 E. I. Du Pont De Nemours And Company Acrylic copolymer composition and adhesive coatings therefrom
US4816500A (en) * 1985-11-25 1989-03-28 E. I. Du Pont De Nemours And Company Two component coating composition of an anhydride containing polymer and a glycidyl component
US4880673A (en) * 1986-03-27 1989-11-14 Bayer Aktiengesellschaft Acrylate binder and its use for dressing leather
US4806600A (en) * 1986-04-15 1989-02-21 Mitsui Toatsu Chemicals, Incorporated Methyl methacrylate syrup composition
US4879364A (en) * 1986-10-20 1989-11-07 The B.F. Goodrich Company Film of carboxylated acrylate latex, and article made therefrom
US4734475A (en) * 1986-12-15 1988-03-29 Ciba-Geigy Corporation Wettable surface modified contact lens fabricated from an oxirane containing hydrophobic polymer
US5322878A (en) * 1987-10-28 1994-06-21 Belland Ag Carboxylated molding copolymers
US5356988A (en) * 1991-07-17 1994-10-18 Cargill, Incorporated Acrylic polymer aqueous dispersion made through a micro dispersion
US5380771A (en) * 1991-07-17 1995-01-10 Cargill Incorporated Aqueous dispersion of amine salts of an acrylic polymer
US5116892A (en) * 1991-07-22 1992-05-26 Eastman Kodak Company Thermosetting powder coating compositions
US5407707A (en) * 1993-11-01 1995-04-18 Ppg Industries, Inc. Powder coating composition based on epoxy containing polymers and polyacid curing agents
US5663240A (en) * 1993-11-01 1997-09-02 Ppg Industries, Inc. Powder coating of epoxy-functional acrylic copolymer and polycarboxylic acid
US5703177A (en) * 1994-12-16 1997-12-30 Ems-Inventa Ag Partially crystalline block copolyester-polyamides
US5844048A (en) * 1995-11-29 1998-12-01 Ems-Inventa Ag Thermosetting powder-type coating compositions
US5872192A (en) * 1995-11-29 1999-02-16 Ems--Inventa Ag Thermosetting powder-type coating compositions
US5905119A (en) * 1995-11-29 1999-05-18 Ems-Inventa Ag Thermosetting powder-type coating compositions
EP0776949A2 (en) 1995-12-01 1997-06-04 Ems-Inventa Ag Heat-curable powder coating
US6313224B1 (en) 1996-02-16 2001-11-06 Ppg Industrial Ohio, Inc. Coating of film-forming resin and functional flow control copolymer
US6013733A (en) * 1996-02-16 2000-01-11 Ppg Industries Ohio, Inc. Coating of film-forming resin and functional flow control copolymer
US6077608A (en) * 1996-09-19 2000-06-20 Ppg Industries Ohio, Inc. Multilayered coating with powder clear coating and substrates therewith and method
US6277917B1 (en) 1996-09-19 2001-08-21 Ppg Industries Ohio, Inc. Powder coating compositions and coated substrates with multilayered coatings
US6251999B1 (en) 1997-12-23 2001-06-26 Ppg Industries Ohio, Inc. Tin carboxylate catalysts for epoxy-acid coating compositions
US5969058A (en) * 1997-12-23 1999-10-19 Ppg Industries Ohio, Inc. Color-plus-clear composite coating composition containing tin catalysts
US6599987B1 (en) 2000-09-26 2003-07-29 The University Of Akron Water soluble, curable copolymers, methods of preparation and uses thereof
US20040265494A1 (en) * 2003-06-25 2004-12-30 Szuping Lu Glycidyl (meth)acrylate powder coating compositions containing caprolactone-derived side chains
US20090227708A1 (en) * 2008-03-04 2009-09-10 Daly Andrew T Epoxy functional acrylic coating powders and powder coatings therefrom having improved filiform corrosion resistance
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